5-arylazo-pyrimidine polyester dyes

ABSTRACT

THE PRESENT INVENTION CONCERNS PROCESSES FOR THE DYEING OF HYDROPHOBIC ORGANIC FIBERS CONSISTING OF LINEAR MACROMOLECULAR ESTERS OF AROMATIC POLYCARBOXYLIC ACIDS WITH POLYVALENT ALCOHOLS, OR OF CELLULOSE ESTER, WITH NEW, WATERDISPERSIBLE BUT ONLY SLIGHTLY WATER-SOLUBLE AZO DYESTUFFS FREE FROM IONOGENIC GROUPS WHICH DISSOCIATE IN WATER HAVING THE FORMULA:   2-(R2-NH-),4-(R1-NH-),5-(A-N=N-),6-(R3-NH-)PYRIMIDINE   WHEREIN   A REPRESENTS CARBOCYCLIC OR HETEROCYCLIC ARYL, ONE OF R1, R2 AND R3 REPRESENTS UNSUBSTITUTED OR NON-IONOGENICALLY SUBSTITUTED PHENYL AND EACH OF THE OTHER R SUBSTITUENTS REPRESENTS HYDROGEN OR ALKYL, CYCLOALKYL OR PHENALKYL, EACH OF THE LATTER THREE SUBSTITUENTS BEING UNSUBSTITUTED OR NON-IONOGENICALLY SUBSTITUTED.   THE PRESENT INVENTION ALSO COMPRISES, AS AN INDUSTRIAL PRODUCT, DYED HYDROPHOBIC ORGANIC FIBERS PRODUCED ACCORDING TO THE DYEING PROCESS OF THE PRESENT INVENTION.

United States PatentOfiFice 3,558,261 Patented Jan. 26, 1971 ABSTRACT OF THE DISCLOSURE The present invention concerns processes for the dyeing of hydrophobic organic fibers consisting of linear macromolecular esters of aromatic. polycarboxylic acids with polyvalent alcohols, or of cellulose ester, with new, waterdispersible but only' slightly water-soluble azo dyestuffs free from ionogenic groups which dissociate in water having the formula:

NH-R 3 wherein A represents carbocyclic or heterocyclic aryl, one of R R and R represents unsubstituted or non-'ionogenically substituted phenyl and each of the other R substituents represents hydrogen or alkyl, cycloalkyl or phenalkyl, each of the latter three substituents being unsubstituted or non-ionogenically substituted.

The present invention also comprises, as an industrial product, dyed hydrophobic organic fibers produced according to the dyeing process of the present invention.

The present invention concerns new, slightly to very slightly soluble azo dyestuffs which are water-dispersible, processes for the dyeing of hydrophobic organic fibers, especially textile fibers consisting of linear, high molecular esters of aromatic p'olycarboxylic acids with polyvalent alcohols or of cellulose esters, andas industrial product,

.dyed hydrophobic organic fibers attained with the new dyestuffs.

It has been found that valuable, water-dispersible, difficultly .soluble azodyestuifs are obtained by coupling the diazonium compound of an amine of Formula I ANH (I) with a coupling component of Formula II NHR,

I N NHR2 N NHR3 (II) to form an an dyestuif of Formula III the components being so chosen that they contain no ionogenic, salt-forming groups.

In these formulae:

A represents a carbocyclic or heterocyclic aryl radical which can contain non-ionogenic substituents, including a phenyl azo group,

of R R and R one R represents an unsubstituted or nonvionogenically substituted phenyl radical and each other R represents hydrogen or anunsubstituted or non-ionogenically substituted alkyl, cycloalkyl or phenalkyl group.

By ionogenic, salt forming groups which are excluded as substituents in the starting components of Formulae I and II and new dyestuffs of Formula III, are meant here and below the known, water solubilising substituents which dissociate acid in water and lend anionic character to the dyestuffs such as sulphonic acid, carboxylic acid, phosphonic acid groups, and onium groups which latter give a cationic character to the dyestuffs, e.g. the ammonium and sulphonium groups; thus rings and substituents defined as non-ionogenically substituted do not contain such groups.

'When A represent a homocyclic aryl radical, this is monoor polynuclear, condensed or uncondensed, particularly it is an unsubstituted or non-ionogenically substituted phenly or naphthyl radical. Preferably A represents a phenyl radical which contains at least one nonionogenic electron-attracting substituent in oand/ or p-position to the amino group and to the azo bond, respectively. As electron-attracting, non-ionogenic substituents it can contain, e.g. the cyano, nitro, thiocyano or trifluoromethyl group; halogens such as fluorine, bromine or chlorine; acyl groups, especially carbacyl groups such as low alkanoyl or low alkenoyl groups, aroyl groups such as benzoyl groups or organosulphonyl groups such as low alkylsulphonyl or arylsulphonyl groups, further sulphonic acid aryl ester groups such as sulphonic acid phenyl, alkylphenyl or halogenphenyl ester groups; carboxylic acid ester groups, e.g. the carbophenoxy group, particularly however optionally non-ionogen'ically substituted carbalsubstituents the radical A can also contain non-ionogenic,

electron-releasing substituents, e.g. low alkyl groups or low alkyl groups mono-substituted, e.g. by a cyano, hydroxy, low alkoxy group or by a halogen such as chlorine or bromine, optionally non-ionogenically substituted low alkoxy groups such as methoxy, ethoxy or ethoXy-carbonylmethoxy groups, phenoxy groups, alkylor halogensubstituted phenoxy groups, or acylamino groups, particularly carbacylamino groups, e.g. low alkanoylamino groups such as the acetylamino group, aroylamino groups such as the benzoylamino group, or low alkylsulphonylamino groups such as the methylsulphonylamino group, or arylsulphonylamino groups such as the phenylsulphonylamino When A contains a phenyl azo group, then in an aromatic car-bocycle, the azo group preferably takes the pposition. The phenyl azo group is preferably unsubstituted; however, it can also be substituted by halogens such as fluorine, chlorine or bromine, low alkyl, low alkoxy groups, or by the nitro group. When A is a phenylazophenyl radical then also the phenylene radical thereof can contain further substituents, e.g. low alkyl or low alkoxy groups, halogens such as fluorine, chlorine or bromine; preferably however, the phenylazophenyl-radical is. unsubstituted.

If A is a naphthyl radical it can be an unsubstituted or a non-ionogenically substituted 1- or 2-naphthyl radical. Here, the principal substituents are low alkyl or low alkoxy groups, halogens such as chlorine or bromine, optionally N-substituted sulphonic acid amide groups, sulphonic acid aryl ester groups, low alkylsulphonyl groups or arylsulphonyl groups.

When A represents the radical of an aromatic heterocycle then it is principally the radical of a 5- or 6-membered heterocycle, preferably containing nitrogen, which belong, e.g. to the pyrazole, thiazole, oxydiazole, thiodiazole, triazole or pyridine series. It can also represent the radical of a polynuclear condensed heterocycle; this then preferably has a fused benzene ring, such as an optionally non-ionogenically substituted benzthiazole, indazole or quinoline ring. Also the fused benzene ring can be substituted by non-ionogenic substituents, especially by halogens, nitro, cyano, thiocyano, low alkyl, low alkoxy, low alkyl-sulphonyl, N-alkylor N,N-dialkyl-sulphamide groups.

In preferred dyestuffs of Formula III, A represents:

(a) A phenyl radical substituted by at least one nonionogenic electron-attracting substituent in and/or p position to the azo bond, or

'(b) A benzthiazolyl-(2) radical optionally substituted by chlorine, a nitro, rhodan, low alkyl, low alkoxy, low alkylsulphonyl or a N-low-alkyl or N,N-di-low-alkylsulphamide group, or

(c) A 4-phenylazophenyl radical optionally substituted by a low alkyl group.

If each of R R and R represents an alkyl radical, then this radical can contain 1 to 8 carbon atoms in a straight or branched chain. Preferably it has 1 to carbon atoms. If this alkyl radical is substituted, then examples of substituents are the hydroxyl group or a low alkoxy group such as the methoxy group, the cyano group or halogens such as chlorine or bromine. As cycloalkyl or phenalkyl groups, R R and R represent, e.g. the cyclohexyl or the benzyl group.

When R R or R represents a phenyl radical, this can be non-ionogenically substituted, e.g. by the non-ionogenic substituents as hereinabove mentioned, especially by halogens such as fluorine, chlorine or bromine, cyano groups,

-low alkyl or low alkoxy groups, by the hydroxyl group,

low alkyl sulphonyl groups, low alkylsulphonyloxy groups, low alkanoyl or low carbalkoxy groups, 10w alkanoylamino or low alkylsulphonylamino groups, unsubstituted sulphamyl or carbamyl groups, sulphamyl or carbamyl groups N-monoor N,N-di-substituted by low alkyl, low

hydroxyalkyl, low alkoxy-low alkyl or low cyanoalkyl groups.

In dyestuffs which are distinguished, among other things, by easy accessibility and high afiim'ty to polyglycol terephthalate fibres and also by extraordinary stability in a boiling dyebath and which, in addition, are fast to sublimation, the coupling components correspond to Formula Ila,

wherein of R R and R one R represents an unsubstituted or non-ionogenically substituted phenyl radical, and the others are hydrogen or identical alkyl groups.

When one of the radicals R R and R is a nonionogenically substituted phenyl radical, the preferred substituents are, e.g. halogens such as chlorine or bromine, low alkyl or alkoxy groups.

Azo dyestuffs according to the invention which are of the formula- NH-RW wherein A represents a phenyl radical substituted by from 1 to 3 electron-attracting substituents in positions ortho and para relative to the azo bridge,

one of R and R represents phenyl substituted by one of the following: hydrogen, lower alkyl, lower alkoxy, and the other of the last-mentioned (Rs) as well as R represent hydrogen and lower alkyl,

are of particularly high affinity for polyethylene glycol terephthalate fibers, and the dyeings obtained therewith on the latter fibers are of especially satisfactory fastness to light.

Very good light fastness is obtained with such dyestulfs of Formula II (b) in which A is of the formula 2-cyano-4-nitro-phenyl, 2,4-dinitrophenyl, 2,4-dinitro-6-chloro-phenyl, 2,4-dinitro-6 bromo-phenyl, 2,6-dichloro-4-nitro-phenyl, Z-nitro-4-methylsulfonyl-phenyl, and 2-nitro-4-ethylsulfonyl-phenyl,

and similar groupings which fall under the formula it a) wherein Z represents nitro, cyano, chloro or bromo Z represents nitro, chloro, bromo or alkyl-sulfonyl, and Z represents hydrogen, chloro or bromo.

The term low as used in this specification and in the appended claims in connection with alkyl and alkoxy means that these radicals have from 1 to 5 carbon atoms, in connection with alkanoyl it means radicals of from 2 to 5 carbon atoms.

The coupling components of Formula II usable according to the invention are produced, e.g. by reacting a phenylamino-dichloropyrimidine of Formula IV NHR I wherein R represents an unsubstituted or non-ionogenically substituted phenyl radical,

with ammonia or with an optionally non-ionogenically substituted primary alkyl, cycloalkyl or phenalkyl amine, at a raised temperature. Preferably this reaction is performed at temperatures of -160 C. in a closed vessel. Phenylamino-dichloro-pyrimidines of Formula IV are ob tained by known methods, e.g. by reacting 2,4,6-trichloropyrimidine with optionally non-ionogenically substituted phenylamines of the Formula RNH The products resulting from the condensation are generally mixtures of isomers of 2-phenylamino-4,6-dichloropyrimidines and 4-phenylarnino-2,6-dichloro-pyrimidines, which are then separated by fractionated crystallization or chromatographic techniques.

The coupling of the diazonium compounds of an amine of Formula I with a coupling component of Formula II is performed by the usual methods, preferably in mineral acid to weakly acid aqueous medium, more especially at a pH of 445. When coupling in a mineral acid medium, the acid is advantageously gradually bulfered, for example, with alkali metal salts of lower fatty acids. It is also possible to simultaneously couple a suitable diazonium compound with a mixture of isomeric coupling components usable according to the invention.

The dyestuffs according to the invention are finely dispersed by milling with surface active dispersing agents.

. 6 Suitable dispersing agents are, e.g. anionic such as alkali The dyestuffs according to the invention are also suitmetal salts of sec. higher alkylaryl sulfonates, alkali metal able for the dyeing of cellulose acetates, polyglycol terephsalts of condensation products of formaldehyde and naphthalates and polyamides the mass. Because of their thalene-sulfonic acids, lignin sulfonates, or non-ionogenic good solubility in organic solvents such as acetone or dispersing agents Such as fatty alcohol p ygly etherschloroform, they can also be used in lacquers and printing When so prepared, the dyestuffs according to the inven- 5 i k tion are Suitable p p y for the dyeing of hydrophobic The following examples illustrate the invention. The Synthetic textile fibers from all aqueous dispersion, temperatures are given therein in degrees centigrade. especially for the dyeing of textile fibers consisting of Polyglycol r h h l t ea th products known by linfial' high molecular esters of aromatic Polycarboxylic the commercial names Terylene, Vycron, Dacron and acids with polyfunctional alcohols, e.g. polyglycol tere- T i phthalaze, polyglycol isophthalate or polycyclohexane diol EXAMPLE 1 tereph alate fibers or consisting of cellulose acetates, e.g. cellulose-2V2 acetate or cellulose triacetate fibers. of 1'ammoz4'dlchlorobenzene are finely (118' The dyestuffs according to the invention can also be peFsed in 300 of W f of hydrochlorif used for the dyeing of synthetic polyamide fibers such as acid and the dlspersion 1S diazotlsed at 0.5 by the addinylon' tion of a solution of 6.9 g. of sodium nitrite in 50 g. of

The dyeing of polyglycol terephthalate fibers with water. A solutronof 20.1 g. of 2,6-b1s-ammo-4 -phenylaqueous dispersions of the dyestuffs according to the inammofpynmldme m 40% acld, added vention is preferably performed at temperatures of over 20 dropwlse to clear, dlazoinum Solutlon obt'flmecl T 0 under pressum above atmospheric The dyeing pH of the reaction mixture 1s then buffered with sodium can also be performed, however, at the boiling point of afzfitate to The yellow couplmg Product the compo the dye liquor in the presence of carriers such as phenyl smon of Whlch corresponds to the formula phenols, polychlorobenzene compounds or similar auxiliaries, or by a pad dyeing process followed by thermofixation at 180-220 c.

Dyestuffs according to the invention have good affinity C1 -N=N NH2 for hydrophobic organic fibers, polyester fibers such as 1 t}; 2

polyglycol terephthalate or cellulose acetate type fibers, preferably the former and, depending on th i i is filtered off, Washed neutral wlth dllute sodium cartion, produce on these fibers strongly colored greenishbonate solution and finally washed free of salt with Water. yellow, yellow, orange, red or claret dyeings which have The d3 is dried in Vacuo at 604m and then milled excellent fastness to washing, milling, sublimation, light, With a mixture of lignin sulphonate and the Sodium Salt crocking, perspiration, solvents, cross dyeing, de ati ing, of a condensation product of naphthalene-Z-sulphonic-acid gas fading and industrial fumes. Moreover, the dyestuffs and formaldehyde. Pure yellow dyeings on polyethylene according to the invention reserve animal and vegetable glycol terephthalate or cellulose triacetate fibres are atfibers well, particularly cotton and wool. Even on closely tained with this dye preparation in aqueous dispersion, Woven fabric or tightly twisted yarn, good and evenly optionally in the presence of a carrier such as the sodium penetrated dyeings are obtained with the dyestuffs accordsalt of o-phenylphenol. The dyeings have very good fasting to the invention. mess to washing, rubbing, light and sublimation.

The dyestufls according to the invention, especially their The 2,6-bis-amino-4-phenylamino-pyrimidine used in isomeric mixtures, differ from previously known dyestulfs this example as coupling component is produced, e.g. by

of similar constitution by their very good drawing powers reacting 2,6-dichloro-4-phenylamino-pyrimidine with aqueand build-up onto polyglycol terephthalate fibers. In addious ammonia at 140l50. The pure compound, obtained tion, dyeings attained with the dyestuffs according to the by crystallisation of the crude product from aqueous ethyl invention have considerably better fastness to light and alcohol, melts at 162163. or sublimation.

Particularly valuable dyestuffs according to the inven- EXAMPLE 2 tion having good fastness to sublimation and excellent A fine Suspension of of fastness to light as well as very good drawing power and boxylic acid ethyl ester in 400 g. of water, 30 g. of 36% build-up are derived from the isomeric mixtures of the hydrochloric acid and 5 g. of cetyl polyglycol ether is Formulae Va and Vb diazotised in the usual way by the addition of 6.9 g. of

I Zl

NH-R3" z, NHR3 (Vb) wherein sodium nitrite at O-5. The diazonium salt solution is clarified and added dropwise, at 5-10", to a solution of Z1 represents the cyan" gmup 20.1 g. of 2,6-bis-amino-4-phenylamino-pyrimidine in 500 mine, Z got 40% acetic acid. The pH of the mlxture 1s then 2232;3 5; 3: 3:23 methyl or ethylsulphonyl group raised to 44.5 by the addition of sodium acetate. On

completion of the coupling, the precipitated yellow pre- Z3 represents hydrogen chlorme or bromme cipitate, the composition of which corresponds to the R represents hydrogen or the methyl group and R and R are identical low alkyl radicals. formula Thus, 2,4-diamino-5-arylazo-6-hydroxyand 6-arninopyrimidines are known as dyes for acrylic fibers. However, f these dyes either do not draw at all on polyester fibers N especially of the polyterephthalate type, or, if they draw CH50Oc N=N I on these fibers, the resulting dyeings fail in important fastness properties that are required of such dyeings by the trade. is filtered off, washed with a large amount of water and dried in vacuo at 6070. After milling with the sodium salt of a condensation product of naphthalene-Z-sulphonic acid and formaldehyde, the dyestuff obtained dyes polyglycol terephthalate fibres from an aqueous dispersion, optionally in the presence of a carrier such as the sodium salt of o-phenylphenol, in pure yellow shades. The dye bath is substantially exhausted. The dyeings have very good fastness to Washing, rubbing, light and sublimation. Also closely woven fabric or tightly twisted yarns are well and evenly penetrated.

Dyestuffs having similar properties are obtained if the diazo components given in column 2 of the following Table I are coupled under the conditions described in the above Example 2 with the equimolar amount of one of the coupling components given in column 3.

precipitate formed, the composition of which corresponds to the formula TABLE I Shade on polyglycoltereph- Diazo component Coupling component thalate fibres Example No.2

3 1-8mil10-2-0hl0l0b8l1281'19 2,6-bis-amino-4'phenylamino- Greenish-yellow.

pyrimidine.

4 1-amino-4-ehlor0benzene. d Do.

5.. l-amino-Z-A-di-bromoben Yellow.

8.. Greenish-yellow.

9 range. 1-am1no-2-n1tro-4-methylbenze Do. l-amino-Znitro-tmethoxybenzene Scarlet. 1-amino-2-nitro-4-chl0robenzene Orange. 1-a.mino-2,4dinitrobenzene D0. l-amin0-2-cyano4-nitrobenzen D0. l-amino-2-bromo4nitrobenzene D0. Lamino-ZA-dinitrofi'ehlorobenzene. D

l-amino-4-acetylbenzene o. Greenish-yellow.

do 2,6-bisam1n me hyl-phenylamino)-pyrimidine. 1-amino-4-benzoy1benzene do Do. o 2,6-bis-a1ninoA-pl1enylamind Do.

pyrimidine. l-aminobenzene-Z-earboxylic acid ethyl ester do Yellow.

2 l-aminobenzene-carboxylic acid butyl ester Do. 2 l-aniizjnobenzenei-carboxylic aeid-fl-methoxyethyl Do.

as er. do 2,6-bis-amino-4-(4'chlorophenyl- Do.

amino)-pyrimidine. l-anugiiobenzene-lcarboxylic aeid-N-methyl- 0 Do.

am e. l-aminobenzeneA-carboxylic acid-N-methyl'N- do Do.

fi-hydroxy-ethylam e. l-aminobenzene3-sulphonie acid-N-ethylamide 2%bis-aznino-4-phenylaminopyrimi- Do.

me. l-aminobenzenei-sulphonic acid phenyl ester do.. Do. 1-ar11ino-4-methyl-sulphonylbenzene do Do. do 2,6-bis-amino-4-(2-methoxyphenyl- Do.

amino)-pyrimidine. 1-amino-2-nitro4-methylsulphonylbenzene do Orange. l-amino-t-ethoxy-carbonylmethoxybenzenc 2,6-bis-amino-4-(2-bromophenyl- Yellow.

amino)pyrimidine. l-ammonaphthalene Reddish-yellow.

2,6-bis-amino-4-phenylaminopyrimidine.

2-aminonaphthalene do l-aminoi-phenylsulphonylbenzene. .-do l-amino-4-aeetylaminobenzene 2,((ii-1bis-amin0-4-phenylaminopyruni- Do.

ne. 37 l-amino-4-fl-acetyloxy-ethylaminu-sulphonyldo Do.

benzene.

EXAMPLE 38 The 2,6-bis-methylamino-4-phenylamino pyrimidine 18.3 g. of 1-amir1o-2,4-dinitrobenzene are dissolved in 100 g. of concentrated sulphuric acid and the solution is diazotised at 20-25 with the amount of nitrosyl sulphuric acid corresponding to 6.9 g. of sodium nitrite. The diazonium salt solution obtained is added dropwise at 0-5 to a solution of 22.9 g. of 2,6-bis-methylamino-4-phenylamino-pyrimidine in 250 g. of 80% acetic acid and 200 g. of water. On completion of the coupling, the red-brown used in the above Example 38 as coupling components is obtained, e.g. by reacting 2,6-dichloro-4-phenylaminopyrimidine with aqueous methylamine at 140-150".

Dyestufis having similar good properties are obtained if a diazo component given in column 2 of the following Table II is coupled with one of the coupling components given in column 3 under the conditions described in the Example 38.

TABLE II Shade on polyglycol tarephthal- Diazo component Coupling component te fibres Example N 0.:

39 l-amino-Z-chlorobenzene 2,fi-bis-n-propylamino-4-phenylamino-pyrimidine Yellow. 40 ..d0 2,6-bis-(fi-hydroxy-ethylamino)-4-phenylamino- Do. 1 pyrimidine.

41 l-amin0-2,4-dichlorobenzene 2,6-bis-n-buty1amino-4-phenylamino-pryimidine- Reddish yellow. 42 .-do 2,6 bis-('y-methoxypropylamino)A-phenylamino Do.

. pyrimidine. 43 l amino-Zfi-dichlorobenzene 2,6-bis-is0pr0pylamino-4-phenylamino- Do.

pyrimidine. 44 1-amino-4-acetylbenzene 2,6-bis-ethylamino-4-(3-methylphenylamino)- Do.

pyrimidine. 45 l-aminobenzenei-carboxylic acid do Do.

methyl ester. 46 l-aminobenzene-i-carboxylic acid-fl- 2,6-bis-ethylamino-4-phenylamino-pyrimidine.- Do.

chloroethyl ester. 47 1-amino-4-nitrobenzene 2,fi-biscyglohexylarnino l-phenylamino- Yellowish-scarlet.

pyrimi me. 48 l-amino-2-nitro-4-methylsulphonyl- 2,6-bis-(B-chloroethylamino)4-phenylamino- Scarlet. benzene. pyrimidine. 49 l-amino-Z-nitrobenzene 2-arm'no-4phenylamino-fi-y-methoxypropylami- Orange.

no-pyrimidine. 50 l-amino-2-chloro4-nitrobenzene 2,6-bis-benzylarnino-4-phenylaminopyrimidine Yellowish-scarlet. 51 1-amino-2-eyano-4-nitrobenzene 2,fi-bis-ethylamino-4-phenylamino-pyrimidine Scarlet. 52.-. 1-amino-2,4dinitrobenzene do Red. 53.- 1-amino-2,4-dinitro-6-chlorobenzene ..do Do. 54 1-amino4-nitro-2-methoxybenzene.- 2,6-bis-prg1pylamino-4-(3-hydroxyphenylamino)- Do.

pyrimi no. 55 1-amino'2-nitro-4-eth0xybenzene 2-benzylamiuo-et-phenylanfinoG-aminopyrimidine. Brownred. 56 1-amino-2-nitro-4-phenoxybenzene 2,dbis-(y-methoxy-propylamino)-4- '-bromo- Do.

- phenylaminoypyrimidine. 1 57.-. I-aDmino-Z-nitro4-ethylsulphonyl- 2,6-bisethylaminoA-phenylamino-pyrimidine.. YelloWish-scarlet.

enzene. 58 .-do 2,6-bis-propy1amin0-4-phenylamino-pyrimidine Do.

EXAMPLE 59 d1chloro-4-(4-methylphenylam1no) -pyr1m1d1ne w1th aque- A fine suspension of 19.7 g. of 4-amino-azobenzene in 30 500 g. of water, 75 g. of 36% hydrochloric acid and 5 g. of oleyl polyglycol ether is diazotised in the usual way at 1520 by the addition of 6.9 g. of sodium nitrite. The clarified diazonium salt solution is added dropwise at ous ethylamine at 140450".

Dyestuffs having similar properties are obtained if a diazo component given in column 2 of the following Table III is coupled under the conditions described in the Example 59 With one of the coupling components given 0-5 to a solution of 27.1 g. of 2,6-bis-ethylamino-4-(4'- 5 in column 3.

TABLE III Shade on polyglycol terephthal- Diazo component Coupling component ate fibres Example No 60.-. 4-amino-azobenzene 2,6-bis-methylamino-4-pheny1amino- Scarlet.

11G. 61- 4-amino-2,3-dirnethyl-azobenzene do D0. 62- o ,oiilfis-aminol-phenylamino-pyrimi- Orange.

e. 63 4-arnin0-4-chloro-2-methyl-azoben do Do.

zene. 64 kamino-azobenzene 2,6-bis-ethylaminoA-phenylamino- Scarlet.

pyrimidine. 65 do- 2,6-bis-('y'methoxy-propylaminoy4- D0.

phenylamino-pyrimidine.

methyl-phenylamino)-pyrimidine in 200 g. of water and 350 g. of 80% acetic acid. The pH of the coupling mixture is then adjusted to 4.5-5 by the addition of sodium acetate. To complete the coupling, the reaction mixture is stirred for 10 hours at 5-10". The red precipitate formed, the composition of which corresponds to the NH- C 2115 is filtered off, washed with water and dried in the usual way. 5 g. of the dyestufi obtained in this Way are brought into a finely dispersed form by milling with 12 g. of sodium salt of a condensation product of naphthalene-2-su1- phonic acid and formaldehyde. With this dye preparation in aqueous dispersion, optionally in the presence of a car rier' such as sodium-o-phenylphenolate, polyglycol terephthalate fibres dyed in pure scarlet shades are obtained The dyeings have very good fastness to perspiration, rubbing and sublimation.

The 2,6 bis ethylamino 4-(4-methyl-phenylamino)- pyrimidine used in this example as coupling component is obtained by the known method, e.g. by reacting 2,6-

EXAMPLE 66 'mineral acid is then buttered by the addition of sodium acetate. On completion of the coupling, the scarlet precipitate formed is filtered oflF, Washed neutral with dilute sodium carbonate solution and then washed free of salt with water. The dried dyestuif, the composition of which corresponds to the formula is an orange coloured powder. A preparation produced by milling it with a lignin sulphonatewhen in aqueous dispersion optionally in the presence of a carrier such as the sodium salt of o-phenyl-phe'nol, dyes polyglycol terephthalate fibres in pure orange shades. The dyeings have very good fastness to washing, perspiration, rubbing and sublimation.

The 2,6 bis amino-4-(3'-chlorophenylamino) -pyrimidine used in the above example as starting material is obtained, e.g. by reacting 2,6-dichloro-4-(3'-chlorophenylamino)-pyrimidine with aqueous ammonia at 140-150.

If, in the above example, the 18 g. of 2-amino-6-methoxybenzthiazole are replaced by a corresponding amount of one of the diazo components given in column 2 of the following Table IV and this is coupled under the conditions described with one of the coupling components given in column 3, then dyestuffs are obtained the dyeings of which have similar good properties on polyglycol terephthalate fibres.

12 acid and 200 g. of water. The pH of the coupling mixture is then adjusted to 45 by the addition of sodium acetate. The dark red coupling product, the composition of which corresponds to the formula TABLE IV Shade on polyglycol terephthal- Dazo component Coupling component ate fibres Example No.1

6 2-amino-5-nitro-thiazole 2,6-bis-amino-4-phenylamino-pyrimidine Scarlet. 68.- ..do 2,6-bis-ethylamino-4-phenylarnino-pyrimidine. Red. 69 22-an1inobenzthiazole 2,6-bis-amino-4-phenylamino-pyrimidine Yellowlsh orange. 70 .-amino-6-methoxy-benz tliiazole Orange. 71.. o Scarlet. 72.. Q-aminofi-rhodanbenzthiazole Red. 73.. 2-amino-6-rhodano-benzthiazo -bis-a uo4-(4-methylp en Scarlet. 74 2-amino-6-cyano-benzthiazole... 2,6-bis-amino-4-phenylamino-pyrimidine Do. 75 2-ariiino-6-methyl-sulphonyl-benzt do Orange.

zo e. 76.- .-d0 2,%lois-('y-methoxy-propylamino)-4-phenylamino-pyrimi- Scarlet.

me. 77.. 2-amino'benzthiazole-fi-sulphonic .-..do Do.

acid-N,N-diethylamide. 2-amino-6-chloro-benzthiazole "do Do. 2-an1ino-6-methoxy-benzthiazole. 2,(bis-n1ethylamin0-4-(4-cyano-phenylamine)-py1'imi- Do.

me. Q-amino-fi-ethoxy-benzthiazole .do D0. Z-amino-benzthiazole... 2,6-bis-n-propylamino-4-phenylan'lino-pyrimidinc Orange. 2,6-b1 hylamin0-4-(2-cyano-phenylamin0)-pyrim1 ine 0. 2,6-bis-isopropylamino-4-(2-carbamyl-phenylamino)- Do.

pyrimidine. 84 1-amino-benzene-4-earboxylie acid- 2,6-bis-methylamino-4-(2-N-methyl-carbamid-phenyl- Reddishethylester. amin0)-pyrimidine. Yellow. 85 .-d0 2,6-his-ethylamino-4-(2'-N-methy1N-B-hydroxyethyl- Do.

earbamid-phenylamino)pyrimidine. 86 l-amino-Z-cyano-benzene 2,6-bis-amino-4-(4-carboethoxy-phenylarnino)pyrimidine Yellow. 87 1-amin0-2-chloro-benzene 2,6-bis-pr0pylamino-4-(3-methylsulphonyl-phenyl- D0.

amino)-pyri.midine. 88 l-amino-2,4-dichloro-benzene 2,6-bis -mgt;hylamino-4-(3-ethylsulphonyl-phenylarnino)- D0.

ynml me. 89 l-afiiirio-btenzene-l-earboxylic acid- 2,6-bis-amino-4-(4-sulphamyl-phenylamino)-pyrimidine... D0.

e 1y -es er. 90 l-amino-benzene-4-sulph0nic acid-(4- 2,6-bis-methylamin0-4-(4methyLsulphamid-phenyl- Reddish methylphenylyester. amino)-pyrimidine. yellow. 91 1-amin0-4-nitr0benzene-2'carboxylic 2,6-bis-a1nino-4-(4-N-methyl-N-B-hydroxyethyl- Orange.

acid-isopropylester. sulphamid-phenylamino)-pyrimidine. 92 1-amino-4-benzoylamino-benzene 2,6-bis-ethylamino4-(3-acetylamino-phenylamino)- Reddish pyrimidine. yellow. 93 Lamina-2,4-dinitr0-benzene 2,6-bis -ar n1i no-4-(3-methyl-snlphonylamino-phenylamino)- Orange.

pyrnm me 94 1-amino-2,4-dinitro-fi-bromobenzene... 2,6-bis-methy1an1ino-4-(3-methylsulphonyloxy-phenyl- Red.

amino)-pyr'nmdine.

EXAMPLE 95 18.3 g. of l-amino-2,4-dinitrobenzene are dissolved in g. of concentrated sulphuric acid and the solution is diazotised at 2025 with the amount of nitrosyl sulphuric acid corresponding to 6.9 g. of sodium nitrite. The diazonium salt solution so obtained is added dropwise at 05 to a solution of 27.1 g. of 4,6-bis-ethylamino-2-(4- methyl-phenylamino)-pyrimidine in 300 g. of 80% acetic optionally in the presence of a carrier such as sodium-ophenyl phenolate. The dyeings have very good fastness to washing, perspiration, rubbing, sublimation and light.

The 4,6-bis-ethylamino-2- 4-methyl-phenylamino -pyrimidine used in this example as coupling component is obtained, e.g. by reacting 4,6-dichloro-2-(4'-methyl-phenylamino)-pyrimidine with aqueous. ethylamine at 1 0 'above example with the coupling components given in column 3 of the same Table.

EXAMPLE 111 21.8 g. of 1-amino-2,4-dinitro-6-chlorobenzene are dissolved in 200 g. of concentrated sulphuric acid and the solution is diazotised at -30 with the amount of ni- TABLE V Shade on polyglycolterephthal- Diazo component Couphng component ate fibres Example Noa 96 l-amino-Z-nitro-benzene 4,6-bis-ammo2-phenyl-ammo-pyrimrdine Yellowlshorange. 97 1-amino-2-nitro-4-methylbenzene Orange. 98 1-amino-2-chloro-4-nitrobenzene -2-phenylammo-pyrnmd1ne Scarlet. 99 l-amino-Z-oyano4-nitrobenzene. 0 Do. 100 l-amino-Z-nitro-benzene-4-methylsulphone 4,6-bis-mefihy1amino-2-(2'-methyl-phenylamino) Do.

pyrrml ne 101 1-amino-4-nitr0-benzene-2-earboxylicaacid-meth- 4,6-bis-isopropylamino-2-(2-chloro-pheny1ami- Do. ylamide. no)-pyrumd1ne. 102 1-amino-2-nitro-benzene-4-earboxylioacid-N- do Do.

methyl-N-fi-hydroxy-ethylamide. 103 l-arninobenzene-i-carboxylic aeid-phenylamide.- 4,6-b1s -amylammo-2-(3-acetylamino-phenyl- Reddishammo-pyrimidine yellow.

EXAMPLE 104 trosyl sulphuric acid corresponding to 6.9 g. of sodium nitrite. The diazonium salt solution so obtained is added dropwise at 0-5" to a solution of a mixture consisting of 22.4 g. of 2,6-bis-ethylarnino-4-phenylaminopyrimidine and 3.3 g. of 4,6-bis-ethylamino-2-phenylamino-pyrimidine in 400 g. of 80% acetic acid and 300 g. of water. On

completion of the coupling, the precipitated dark red coupling product, the composition of which corresponds to the formulae $1 NH- CzHs addition of sodium acetate. On completion of the coupling, the precipitated red coupling product, the compositio of which corresponds to the formula NH-CaHy C aO diazo components given in column 2 of the following.

Table VI are coupled under the conditions described in the above example with the equivalent amounts of the coupling components given in column 3 of the same table.

TABLE VI NEE-C2115 is filtered off, washed with water and dried in the usual way. 10 g. of the mixture of dyestuffs so obtained are brought into a finely dispersable form by milling with 20 g. of a lignin sulphonate.

Polyglycol terephthalate fibres and cellulose triacetate fibres can be dyed in pure red shades with this dye preparation from an aqueous bath, optionally in the presence of a carrier such the sodium salt of o-phenylphenol. The dyeings have very good fastness to Washing, perspiration, rubbing, sublimation and light.

The mixture consisting of 4,6-bis-ethylamino-Z-phenylamino-pyrimidine and 2,6-bis-ethylamino-tphenylaminopyrimidine used in this example as coupling component is obtained, eg, by condensation of 2,4,6-trichloro-pyrimidine with one equivalent of aniline andv subsequent reaction of the condensation products with at least four equivalents of diethylamine at 150-155 Dyestuffs having similar properties are obtained when the equivalent amount of any one of the diazo components given in column 2 of the following Table VII is coupled with any of the mixtures of coupling components given in column 3 of the same table.

Shade on polyglycolterephthal- Diazo component Coupling component ate fibres Example N0.:

105...; Z-amino-E-nitrdthiaZole 4,6-bis-isopropylamino-Z-phenylamino-pyrimidine Red. 106... 3-amino-5-nitro-indazole do Orange. 107 5-amine-1-phenyl 3-methyl-pyrazole 4,6-bis-amino-2-(2-methoxy-phenylamino)pyrimidine". Yellow. 103... 4-amino-quinoline do Scarlet. l0

4-amino-azobenzene 4,6-bis-rnethylamino-2-(4-chlorophenylamino)pyrimidine- I50. 0.

110 4-arm'no-2,3-dimethyl-azobenzene ..do

TABLE VII Shade on polyglycolterophthal- Diazo component Coupling component ate fibres Example N 0.:

112 Lamina-2,4-dinitro-benzene 22.4 g. 2,6-bisethylamino-4-phenylaminopyrimidine; 3.3 g. 4,6-bis- Red.

ethylamino-2-phenylaminopyrimidine. 1-amino-2'cyano4-nitro-benzene do Scarlet. 1-amin0-2,6-diehloro-4-nitrobenzene... do Do. 1-amino-2-nitrobenzene Orange. 1-amino-4-nitrobenzene Do. 1-arnin0-4-nitrobenzene-2-earboxylic aciddo Scarlet.

ethylcster.

118 l-amino-4-nitrobenzene2-carboxylic acid-amide do Do.

119 1-amino4-nitrobenzene-2rea.rboxylic aeiddo D0.

methylamide.

120 l-amino-4-nitrobenzene-2-earboxylie acid- .d0 D0.

dimethylamide.

121 l-aminM-nitrobenzene-Z-carboxylic acid-fido Do.

hydroxyethylamide.

122 l-amino-2-nitrobenzene-4-carboxylio aciddo Do.

butylester.

123 1-amino-2-nitrobenZene-4-carboxylic acid-N- do Do.

methyl-N-phenylamide.

124 l-amino-Z-nitrobenzene-4-su1phonie acid-N- 22.4 g. 2, 6-bis-ethy1amino-4-phenylarninopyrirnidine; 3.3 g. 4, 6- Scarlet.

methyl-N-fl-hydroxyethylamide. bis-ethylamino2phenylamino-pyrimidinc.

125 1-amiuo-2-nitro-benzeneA-sulphonic ao1d-4- .do Do.

methyl-phenylester.

126 l-amino-2-nitro-4-methylsulphony1-benzene do D0.

127 do .1 17.5 g. 2, G-bis-arnino4phenylamino-pyrimidine; 2.6 g. 4, 6-bis- Orange.

amino-2-pheny]amino-pyrimidine.

128 1-amino'2-nitro-benzene-4-sulphonic acid-amide 25 g. 2, fi-bis-n-propyl-amino-4 phenylamino-pyrimidine; Scarlet.

3.5 g. 4, 6-bis-n-propylamino-2-phenylamino-pyrimidine.

129 1-amino-2-nitro-benzeneA-sulphonic acid- 27 g. 2, fi-bis-butylaminoA-phenylamino-pyrlmidine; 4.1 g. 4, 6- Do.

methyl-amide. bis-butylamino-2-phenylamino-pyrimidine.

130 1-amino-2-n1tro-benzene-4-su1phonie acid-'y- 30 g. 2, 6-bis-isoamyl-amino4-phenylamino-pyrirnidlne; 4.1 g. D0.

methoxy-propylamide. 4, fi-bis-iscamyl-amino2-phenylamlno-pyr1midme.

131 1-amin0benzene-4-carboxylic acid ethylester- 38 g. 2, fi-bis-rmctyl-amino-4-phenylamino-pyrimidme; 4.5 g. Reddish- 4, 6-bis-n-octyl-amino-4-phenylamino-pyrimidine. yellow.

132 l-aminobenzene-4-sulphonlc aoid-y-methoxy- 16.6 g. 2, 6-bis-arnino-4-(2-methylphenylamino)-pyrimidine; Reddishpropylamide. 5 g. 4, 6-b1s-amino2-(2-methylphenylamino)-pyr1midine. yellow.

133 1-aminobenzene-4-sulphonie acid-N-methyl-N- 23 g. 2, G-bis-B-hydroxyethylamino-4-(2-methylphenylamlno)- Do.

phenylamide. pyrimidine; 7.3 g. 4, 6-bis-fl-hydroxyethylammo-2-(2- methylphenylarnino)-pyrimid1ne.

134 1-a1nino-4-methyl-sulphonylaminobenzene c. 27 g. 2, G-biS-y-methoirypropy1amino-4-(2-methylphenylamlno)- D0.

pyrimidine; 9 g. 4, 6-bis-'y-methoxypropylamino-2-(2- methylphenylamino)-pyrimidine.

135 1-amino-4-(4-methylphenyl)-sulphonylamino- 26 g. 2, 6-bis-/8-chloroethyl-amino-4-(2-methyl-phenylamino)- Do.

benzene. pyrimidine; 8.5 g. 4, 6-bis-fi-chloroethy1-amino-2-(2-methylphenylamino)-pyrirn1dine.

136 4-amino-azobenzene 18.5 g. 2, 6-bis-methylamino-4-(2'-methyl-phenylamlno)- Scarlet.

pyrimidine; 5.5 g. 4, 6-bis-methylamino-2-(2-methyl-pheny1- amino)-pyrimidine.

137 4-amin0-3-chloro-2-methyl-azobenzene 17.6 g. 2, 6-bis-amlno-4-(3-Inethy1-phenylamlno)pyrimidine; Rcddish- 3.9 g. 4, 6-bis-amino-2-(3-methyl-phenylamino)-pyr1mid1ne. orange.

138 4-amino-4-nltro-azobenzene 29 g. 2,6-bis-lsoamylaminM-(W-methyl-phenylamino)-pyrimid1ne; Scarlet.

3.5 g. 4,6-bis-isoamylamino-2-(3-n1ethyl-pheny1amino)-pyrimi- 139 4-am1no-2-methyl-5-methoxy-azobenzene 25.5 g.2,6-bis-fl-eyanoethylamino-41(im'methylphenylamino):pyrim- Do.

idine; 6.6 g. 4,6-bis-fi-cyanoethylarnmorz-(arrnethylphenylamino)-pyrimidine.

140 2-amino-5-methyl-thiodiazole-(1,8,4) 18 g. 2,6-bis-amin0-4-(4-methylphenylamino)-pynmidine; 3.5 g. Orange.

4,6-bis-an1ino-2-(4-methylphenylarnino)-pyrimidine.

141 5-amino-1,3 di-methyl-pyrazole d0 Yellow 142 5amino-1-phenyl-3-methyl-pyrazole do D0.

143 4-amino-quinoline 20.2 g.2,6b1s-methy1arnino-4-(4-methylphenylam1no) pyrlmldme; Scarlet.

13.6 g. 4,6-bis-methylamino-2-(4-methylphenylamino)-pyrimi 144 2-amino3-nitro-5-acety1-thiophene do Orange.

145 3-amino-indazole do Reddish yellow.

146 3-amino-5-nitro-indazole do Orange.

147 3-amino6chloro-indazole do Reddish yellow.

148 6amlno-indazole do Yellow.

149 2-amino-1-methyl-triazole-(1,3,5) 20.2g.2,6-bis-methylamino4-(4-methylphcnylamino)-pyrimidine; Yellow.

3.8 g. 4,6-bis-methylamino-2(4-methylphenylamino)-pyrimime. 2-amino-6-methoxy-benzthiazole do. 2-amino-5-nitro-thiazole do 152 1-amino-2-chlor0-benzene g. 2, methoxy-phenylpy g. 4,6-bis-amino-2-(4-methoxy-phenylamin0)-pyrimid1ne. 153 2-amin1o-naphthalene-5-sulphonic acid-methyldo Scarlet.

am! e. 154 1-amino-2,4-dinitro-6-chlore-benzene 19 g. 2,6-bis-ethylamlno-4-(4-methoxy-phenylamino)-pyrimidine; Bordeaux.

. 9.7 g. 4,6-bis-ethylamino-2-(4-methoxy-phenylamino)-pyrimidine.

155 1-an1ino-2,4dinitro-benzene do Do.

156 l-amindZ-nitro-benzene 18 g. 2,6-bis-ethylamino-4-(4-chlorophenylamino)-pyrinu ine; 11.2 Orange.

g. 4,6-bis-ethylamino-2-(4-chl0r0phenylamino)-pyrimidine.

157 1-amino-2,4-diuitro-benzene 20.2g.2,6-bis-methylamino-4-(4-methylphenylamino)-pyrimldine; Red.

dj g. 4,6-bis-methylarnino-2-(4-methylphenylamino)-pyrimime. 158 1-amino-2,4-dinitro-6-chloro-benzene do D0.

EXAMPLE 159 20 parts by welght of triethanolamme,

20 parts by weight of octylphenol polyglycol ether, and Polyglycol terephthalate fabric (such as Dacron of 900 Parts b wgight of t E. I. du Pont de Nemours, Wilmington, DeL, USA.) is 7 impregnated in a foulard at 40 with a liquor of the following composition:

The fabric is wrung out to a liquor content of about 100% dried at 100 and the dyeing is then fixed for 30 seconds at a temperature of 210. The dyed goods are 20 parts by Weight of the dyestufi according to Example rinsed with Water, soaped and dried. Under these condi- 59, finely dispersed in tions, a scarlet dyeing is obtained which is fast to wash- 7.5 parts by weight of sodium alginate, 75 ing, rubbing, light and sublimation.

1 7 The dyestufis described in the other examples produce dyeings of equal quality according to this process.

EXAMPLE 160 In a pressure dyeing apparatus, 2 g. of the dyestuff obtained according to Example 38 are finely suspended in 2000 g. of water containing 4 g. of oleyl polyglycol ether. The pH'of the dyebath is adjusted to 5-5.5 with acetic acid.

100 g. of polyglycol terephthalate fabric are then introduced at 50, the bath is heated to 140 within 30 minutes and dyeing is performed for 50 minutes at this temperature. The dyeing is then rinsed with water, soaped and dried. Under these conditions, a pure red dyeing is obtained which is fast to washing, perspiration, light and sublimation.

The dyestuffs described in the other examples produce dyeings of equal quality by this process.

EXAMPLE 1 61 2 g. of the dyestuff obtained according to Example 111 are dispersed in 4000 g. of water. 12 g. of sodium phenyl-phenolate are added to this dispersion as carrier and also 12 g. of diammonium phosphate are added and 100 g. of polyglycol terephthalate yarn are dyed for 1%. hours at 95-98". The dyeing is rinsed and aftertreated with dilute sodium hydroxide solution and a dispersing agent.

In this way a pure red dyeing which is fast to washing, light and sublimation is obtained.

in the above example, the 100 g. of polyglycol terephthalate yarn are replaced by 100 g. of cellulose triacetate fabric, dyeing is performed under the conditions given and the dyeing is then rinsed with water, a red dyeing is obtained which has very good fastness to washing and sublimation EXAMPLE 1'62 Polyglycol terephthalate fabric (such as Dacron of E. I. du Pont de Nemours, Wilmington, Del, U.S.A.) is impregnated in a foulard at 40 with a liquor of the following composition:

20 parts by weight of the dyestuff'acording to Example 113, finely dispersed in 7.5 parts by weight of sodium alginate,

20 parts by weight of triethanolamine,

2-0 parts by weight of octylphenol polyglycol ether, and

900 parts by weight of water.

The fabric is wrung out to a liquor content of about 100%, dried at 100 and the dyeing is then fixed for 30 seconds at a temperature of 210. The dyed goods are rinsed with water, soaped and dried. 'Under these conditions, a scarlet dyeing is obtained which is fast to washing, rubbing, light and sublimation.

We claim:

1. A composition of matter comprising (a) a fibrous material consisting essentially of fibers of linear high molecular ester of an aromatic polycarboxylic acid with a polyvalent alcohol, and

(b) an azo dyestuff free from ionogenic groups which dissociate in water, of the formula NIH-R NH-R wherein A represents carbocyclic or heterocyclic aryl, one of R R and :R represents unsubstituted or nonionogenically substituted phenyl and 18 each of the latter three being unsubstituted or nonionocycloalkyl or phenalkyl, each of the latter three being unsubstituted or nonionogenically substituted, 5 2. A composition of matter comprising (a) a fibrous material consisting essentially of fibers of cellulose triacetate, and (b) an azo dyestutf free from ionogenic groups which dissociate in water, of the formula A represents carbocyclic or heterocyclic aryl,

one of R R and R represents unsubstituted or nonionogenically substituted phenyl and each of the other Rs represents hydrogen or alkyl,

cycloaklyl or phenalkyl,

each of the latter three being unsubstituted or nonionogenically substituted.

3. A process for the coloring of organic material selected from a fibrous material consisting essentially of fibers of linear macromolecular esters of aromatic polycarboxylic acids with polyvalent alcohols, a fibrous material consisting essentially of fibers of cellulose acetate, a fibrous material consisting essentially of synthetic polyamide fibers, comprising dying the said fibers with an aqueous dispersion of an azo dyestuif free from ionogenic groups which dissociate in water, of the formula A represents carbocyclic or heterocyclic aryl,

one of R R and R represents unsubstituted or nonionogenically substituted phenyl and each of the other Rs represents hydrogen or alkyl, cycloalkyl or phenalkyl,

each of the latter three being unsubstituted or nonionogenically substituted.

4. A process according to claim 3, wherein the fibrous material consists essentially of fibers of linear macromolecular ester of an aromatic polycarboxylic acid with a polyvalent alcohol.

5. A process according to claim 3 wherein the fibrous material consists essentially of the fibers of cellulose triacetate.

6. A process according to claim 3 wherein the fibrous material consists essentially of synthetic polyamide fibers.

References Cited UNITED STATES PATENTS 3,042,648 7/1962 Lewis 260-454 3,177,214 4/1965 Sulzer et a1. 260-154 3,341,512 9/ 1967 Wegmuller et a1 8-26 NORMAN G. TORCHIN, Primary Examiner J. E. CALLAGHAN, Assistant Examiner US. Cl. X.R.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. g 5 53 2 1 Dated lamlan; 2 91] Inventor-(s) Hans Ackermann et a1 It is certified that error appears in the above-identified paten' and that said Letters Patent are hereby corrected as shown below:

In the heading to the printed specification after line 6 insert assignors to J. R. Geigy AG, Basel, Switzerland after line 7, insert Claims priority, application Switzerland 10857/65 August 2, 1965 Signed and sealed this 22nd day of August 1972.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer Commissioner of Patent FORM PO-1050 (10-69] USCOMM DC a u.s. covnuunn "mamas orncz: nu 

